Carbon remover and metal surface cleaning composition



Patented Apr. 5, 1949 orrlca CARBON REMOVER AND METAL SURFACE CLEANINGCOMPOSITION Ben Box-us, St. Louis, Mo., assignor to Shell DevelopmentCompany, San Francisco, Call! a corporation of Delaware No Drawing.Application May 5, 1947, Serial No. 746,153

3 Claims. (CL 252-118) This invention relates to the removal ofundesirable foreign deposits from metal surfaces. More particularly thisinvention pertains to the removal of hard carbonaceous materials,resins, varnish, lacquers, rust, abrasives, welded metal particles, andthe like, from engines, turbines, industrial equipment and the like byapplying thereto a novel chemical composition, each component thereofbeing within rather specific proportions, said composition having theability of penetrating through the deposit, loosening it andfacilitating in removing it from the metal surface, leaving the engineor other metal surfaces clean and undamaged.

The development of high power engines operating at relatively very hightemperatures and heavy loads, such as internal combustion engines,

Diesel engines, gasoline aircraft engines, jet

engines, form, during their operation, carbon and sludge deposits whichcause sticking, clogging, and wear of movable parts. This results inwear and corrosion of engine parts, and generally reduces the operatingefliciency of the engine.

Present developments in gas turbine engines which operate at suchelevated temperatures as from 1100 F. to 1800 F. greatly accentuate thisproblem. Thus, gas turbine engine parts such as the compressor bladesand turbo-jet units such as turbo-super charged engines as well as otherindustrial units such as heat exchange elements, torque convertertransmissions, air and gas compressor valves, etc., become coated withinrelatively short periods of time with thick layers of carbonaceous andother foreign deposits which must be removed. These deposits adhere sotenaciously to the surface that the only way to remove them at presentis by hand scraping or by soaking in chemical solutions for long periodsof time. Such drastic treatment usually results in damage caused bycorrosion or pitting of the treated metal surface due to the chemicalnature of the material used to remove the deposits, swelling ordestruction of insulating and non-metallic parts, andchipping orcracking of metal surface due to hand scrubbing and cleaning. Inaddition present known deposit removers are highly toxic due to theirhigh content of 2 phenolic and/or halogen-containing materials which area hazard and are detrimental to the health of the user. Known depositremovers also introduce a fire hazard problem due to the fact that suchmaterials have low flash points but are only effective at elevatedtemperatures.

It is an object of this invention to provide a cleaning anddeposit-removing composition which can be easily and readily applied toheavily carbon-coated metal surfaces at room or at slightly elevatedtemperatures and leave the surface clean and rust proofed. It is anotherobject of this invention to provide a cleaning composition which isnon-corrosive to the metal being cleaned and which is non-reactive withnonmetallic parts with which it might come in contact. Still anotherobject of this invention is to provide a cleaning composition which issafe to use within a relatively wide temperature range, and isnon-toxic.

The above and other objects may be attained in accordance with thepresent invention by admixing, with a suitable hydrocarbon base, certainchemically active ingredients in rather specific proportions, each ofwhich exerts a specific function and a co-ordinating one with thecomposition taken as a whole which results in a potent cleaningcomposition. The active ingredienm of this invention comprise ahydrocarbon base admixed with specific types of detergent, wetting andcoupling agents, a penetrant and water, all of which are essential. Acriteria of compositions of this invention is that all ingredients whichcomprise it must be present at all times and in relatively specificproportional relationship to each other.

The base comprises essentially a hydrocarbo having a boiling point abovethat of room temperature and up to boiling temperatures of minerallubricating oil fractions. The selection of the type of hydrocarbon baseto be used depends primarily upon the intended use of the composition.Thus, if the composition is to be used mainly as a carbon remover, arelatively light petroleum hydrocarbon fraction, such as kerosene, ispreferred, although mineral seal oil, gas oil, various petroleum naphthacuts, mineral 4 amounts varying from 2 to 15% and generally is keptbetween about 4 to 8% by weight.

The function of a good penetrant is to penetrate through interferinglayers of deleterious materials and loosen them from the surface towhich they adhere. To accomplish this a penetrant must possess lowdegree of volatility, low surface tension and high capillary or creepingproperties so that once having penetrated as a mineral lubricating oilshould be used. The

amount of base used can vary from between about 12% to about 50% byweight, and preferably between about 12% and 20% by weight of thecomposition.

Detergents of this invention function both in a chemical and physicalmanner. help to keep finely divided carbon and resinous particles formedduring operation of internal combustion engines, turbines and the likeor deposits already formed but loosened from a surface by suitablemeans, in a state of suspension thereby preventing their adherence to orbuildup on a surface. This is due to the adsorptive action of thedetergents, making the carbon particles and other deleterious matterwith which they. come in contact large enough and light enough so thattheir settling rate is greatly retarded and therefore they tend toremain in suspension. with other constituent materials of this inventionso as to aid in loosening and removing deposits from surfaces and at thesame time not interfere with the activity of other additives present.They are also thermally stable, resist oxidation and attack by activecorrosive materials.

It has been found that only a limited number of detergents have theabove properties when employed in conjunction with other additives ofthis invention. Broadly they include the amine and ammonium salts oforganic and inorganic acids, as well as the alkali metal salts thereof.They can best be formed by combining salts of primary, secondary andtertiary amines containing from about 8 to about 20 carbon atoms, e. g.octyl, nonyl, undecyl, stearyl, dibutyl, diamyl, dioctyl, didecyl,triethyl, tributyl amines; alkylolamines, e. g. mono-, diandtriethanolamine, diethylethanolamine, dimethylethanolarnine,monoethylethanolamine, phenylethanolamine, phenyldiethanol amine, ethylphenylethanolamine, mono-, diand-triisopropanolamine; heterocyclicamines, e. g. morpholine, methyl morpholine, ethyl morpholine, phenylmorpholine; cyclic amines, e. g. cyclohexylamine,dicyclohexylamine; andammonium and alkali metals, e. g. sodium, potassium, lithium, with thefollowing acidic materials: saturated and unsaturated fatty acidscontaining up to about 20 carbon atoms, terpene acid derivatives such asabietic and rosin acids, naphthenic and sulfonic acids as well asinorganic acids such as phosphoric acid and the like. The followingdetergents are particularly suitable for use in this invention:diethylethanolamine .oleate, diethylethanolamine stearate, laurylamineacetate,laurylamine stearate, laurylamine abietate, laurylaminenaphthenate, laurylamine ricinoleate and laurylamine phosphate;morpholine oleate, ethyl morpholine oleate, morpholine stearate,morpholine naphthenate; cyclohexylamine ricinoleate, cyclohexylaminephosphate; ammonium ricinoleate; sodium petroleum sulfonate, etc. Thedetergent is used in Primarily they In addition the detergents co-actthrough the foul matter adhering to a surface it can displace ittherefrom and leave on said surface a protective oiliness film which ifdesired can be easily removed by flushing, for example, with steam andthe like. The protective film acts as a boundary separator betweencontacting surfaces thereby protecting them from wear and the like.Penetrants which are particularly suitable due to their co-ordinateaction with other constituents of this invention so as to produce aproduct having maximum efiiciency in removing foul matter from surfacesare halogenated aliphatic and aromatic compounds, e.g.trichloroethylene, 2,2-dichloroethylether, O-dichlorobenzene,dichloroisopropylether, etc.; ketones, eIg. mesityl oxide, isophorone;and mixture of the above halogenated compounds and ketones. Thepenetrant generally comprises approximately 20% to 40% by weight of thecomposition.

To activate and improve the general properties of compositions underconsideration a wetting agent is employed which co-acts with the abovepenetrants and wets the surface which has been rendered free of thedeleterious materials by the active ingredients of this composition. Thesurface thus'wetted is protected and foul matter is prevented fromre-adherlng to the cleaned surface. Wetting age ts which are suitablefor this purpose are alkyl and alkyl substituted alkylol amines; cyclicamines; heterocyclic amines; alicyclic alcohols, etc. These types ofcompounds can best be illustrated by' such specific compounds asdiethylethanolamine, laurylamine, morpholine, ethyl morpholine,cyclohexylamine, cyclohexanol, trimethylcyclohexanol and the like. Theamines are particularly preferred, for in addition' to acting as wettingagents, they react with acidic materials thereby continuouslyreplenishing the detergent agent. The amount of wetting agent usedranges between about 2% and about 25% and preferably is kept within 8%to 20% by weight of the total composition.

Water is an essential component of the present composition. The exactfunction or mechanism of it is not understood, but in cases where waterwas eliminated as a component of the present composition the efliciencyof the latter as a deposit remover was reduced to such a degree as torender it almost useless. It is noted that the wetting power of thecomposition is increased and the foreign matter is kept in a morepermanent dispersion due to the presence of water. It therefore appearsthat water exerts a synergistic effect and also acts as a carrier forforeign deposits loosened from. a surface. The amount of water usedvaries from between about 10% to about 20%, and preferably is keptbetween about 12% and 15 %by weight.

In order to stabilize compositions under consideration so as to preventseparation and break down, a coupling agent is added. The preferablecoupling agents are polyhydric organic derivativessuch as alkyleneglycols; dlglycols, e. g.

dipropylene glycol, dibutylene glycol,.diamylene glycol; triglycol, e.g. tripropyleneglycol; ether mimosa.

alcohols containing upto 20 carbon atoms jand more particularly glycolmono-alkyl ethers. e. g. the cellosolves,.e. g. ethylene glycolmono-ethyl ether, ethylene glycol mono-proply ether, ethylene glycolmono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycolmono-tert.butyl ether, ethylene glycol mono-hexyiether, propylene glycolmono-ethyl ether, propylene glycol mono-isobutyl ether, etc.; diglycoimono-alkyl ethers such as the carbitols', e. g. diethyleneglycolmono-methyl ethyl, normal and isopropyl ethers,

To test the effectiveness of composition of this invention as removersor carbon and other "deleterious materials from various surfaces thefollowing tests were performed and results come pared with the bestknown commercial materials.

used for the same purpose.

' I Example I Steel panels were sprayed with a solution of oil sludge incarbon tetrachlorideand baked at 220? C. in a forced draft oven. Thesteel panels werethen removed from the oven, cooled and some wereimmersed indeposit remover compositions of this invention while otherswere im-.

mersed in commercial deposit remover X reportedv to contain chlorinatedaromatic, water, 'butyl cellosolve and ethanolamineoleate. The time ofinitial deposit removal as well as time of complete removal were notedat room temperatures and at approximately 185 F. In cases where completeremoval of the deposit was not eflfected in minutes, the test wasstopped and the percent of depositremoved was estimated aswell as theeflect of flushing the test piece with water noted.

' Temper- Time of Initial Time oi Complete Appearance after waterComposmml ature Removal Removal flush F. 1 Commercial Productx.-. 185None after 1l|r. No eflect, Panel still Composition of Ex. 1 Compositionof Ex. 2 Composition oi Ex. 3 Composition of Ex. '4

None alter 2 hrs...

corroded with heavy deposit.

Panel absolutely clean.

Do. Do.

% and is preferably kept in the range of- 15 The above classes ofadditives which constitute the essential component parts of compositionsof this invention have not been selected at random but have beenselected after careful and painstaking research and because of theircoordinating action in aiding to remove deleterious engine depositsaswell as removal of undersirabie foreign deposits from various surfacesin general.

To more fully illustrate the present invention Example 11' Theeifectiveness of the present deposit removers was tested on pancakevalves from a 'cated in the table the temperature Wasmainthe followingare a few compositions which have been compounded, tested and foundextremely of the deposits was observed after the valvestained'at about120 F. The time for removal were steam flushed.-

Com sition Tern r- Time of carbon removal Appearance of valves p0 sta rafter flush treatment 1 comers Product ii in: .Yi'ftffi.Fiffi'iifiifilflffi'l.ff:::::13:33:: :3?"

Boom 2 hr. for substantial complete carbon removal... Valves were cleanexcept 2 Product oiEx. 1.r. ioraiewspecks.

. 120 F. 14hr. for complete carbon removal Valves were perfectly clean.3 Hand scraping 2 valves required 1 day ano naphthenic sulfonateeflicient for removing deposits from metal surfaces and the like.

. ages:

l trimethyl cyclohcxm amonium ricinoleate water 1 hiw'ih'iiiifa areparts by weight.

Example I" After a 500 hour test run of a GM-Vl single cylinder Dieselengine the piston rings were covered with heavy fouled deposits. Thepiston rings were immersed at room temperature in a composition of thisinvention and in a commercial product X and the time required forloosening and removing the fouled deposits noted.

minutes and valves and BMGQOSB E'zample IV The effectiveness of depositremovers of this invention was tested on hydrocarbon compressors,

equipment was by. sanding with fine emery cloth and requiredapproximately 8 hours of sanding by one man to clean the cylinder wallsalone and of an hour to scrape a valve clean. The time which vwasrequired to clean five cylinders with a composition of Example 1 wasonly 10 to 12 pistons were perfectly cleanafter a 10 minute soaking in acomposition of Example 1 at room temperature and a one minute steamflush.

Example V i A, gas turbine eng e was run for a number of days untilheavy fouling of the axial flow compressor was noted. The engine was cutdown to about half speed and sprayed at room temperature into the airintake of the compressor during a 4 minute interval with 10 gallons of acomposition of this invention referred to in the tabl as Example 1. Thiswas followed by steam flushin the engine and it was observed that thecompressor was absolutely clean. In addition the overall engineefiiciency of the clean engine increased by about 5.8% for a two hourperformance test. Previous methods of cleanin such engines necessitatedtearing it down which took about 24 to 32' hours and requiredapproximately 32 hours to clean.

Example VI thereto or otherwise harmful effect-when in contact with theskin.

rubber, plastic surfaces and the like and can be applied by any knownmeans such as spraying. immersing, di ping, swabbing, and the like.

It is to be understood that while the features of the invention havebeen described andillustrated in connection with certain specificexamples, the invention, however. is not to be limited restricted,except by the prior art and the scope of the appended claims.

I claim as my invention:

1. A cleaning composition comprising a mix- "ture of R Per cent byweight Kerosene V 12 o-Dichlorobenzene' 40 'Dlethylethanolamine oleate 6Diethylethanolamine 2 Ethylene glycol monobutyl ether 10 Water 12 2. Acleaning composition comprising a mixture of about 12% to about 50% ofkerosene, about 2% to about 15% of diethylethanolamine oleate. about toabout 40% oif o-dichlorobenzene, about 2% to about ofdiethylethanolamine, about 10% to about 20% of ethylene glycol monobutylether, and about 10% to about 20% of water.

3. A cleaning composition comprising a mixture of about 12 to 50%kerosene, about 2 to 15% of diethylethanolamine oleate, about 20 to of achlorinated organic compound selected from the class consisting ofo-dichlorobenzene, trichloroethylene, dichloroethyl ether anddichlorinvention at both room temperature and 185 F.

perfectly clean. The commercial product was still ineffective at the endof the test period.

Compositions of this invention are excellent for fective in removingdirt and grease from indus- .trlal equipment. They are non-corrosive,nonstripped the paint off the steel panel leaving it v isopropyl ether,about 2"to'25%of a diethylethanolamine, about 10 to 20% of ethyleneglycol monobutyi ether-and about 10 to 20% water.

nan BQRUS.

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2,032,174 Johnson Feb. 25, 1936 2,244,721 Mitscherling June 10, 19412,303,551 Houghton Dec. 1, 1942 2,383,114 Villiers Aug. 21, 19452,398,242 Morgan Apr. 9, 1946 2,404,297 Kroll July 16, 1948 toxic andare not a fire hazard. They have no

